DE2847986A1 - METHOD FOR PRODUCING POWDER-SHAPED, THERMOPLASTIC COPOLYMERS FROM AETHYLENE AND BUTEN- (1) - Google Patents

Description

- 3 -.
Gelsenkirchen-Scholven, September 20, 1978

VEBA-CHEMIE AKTIENGESELLSCHAFT Gelsenkirchen-Buer

Process for the production of powdered thermoplastic Copolymers of ethylene and butene- (l)

Description and examples

The invention relates to a method for producing thermoplastic Copolymers of low density ethylene as processable powders of relatively high bulk densities by copolymerization of ethylene and butene- (l) with the help of vanadium-containing Ziegler catalysts.

The preparation of Äthylenpolymerisaten low density is usually prepared by polymerization of ethylene with free-radical initiation under high pressures of 1 000 bar · bar 3 000 '"*. These methods are again associated with the disadvantage that the generation of high pressures technically complicated and costly Another disadvantage of these processes is that they cannot be used to produce polymers with such high molecular weights that they have satisfactory properties such as good stress cracking resistance to surface-active media or high breaking strength under alternating bending stress and others are therefore not suitable for all areas of application because of their relatively low molecular weights.

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Furthermore, a process has become known for the production of low-density polyethylene with densities of 0.915 g / cm- ⁵ to 0.930 g / cm ^ by copolymerization of ethylene with (l) -olefins in hexane at temperatures> 130 ^° C. In this process, it is the disadvantage that the polymer is obtained dissolved in hexane and has to be separated from the solvent.

Recently, a process has become known through Belgian patent 862,697, in which ethylene and optionally (l) -olefins as comonomers by polymerization with vanadium-containing catalysts in inert liquid hydrocarbons at temperatures from 50 ^° C. to about 95 ^° C. and pressures from 10 bar to 100 bar powdery polymers with excellent properties for further processing into finished parts can be produced. Suitable diluents in the polymerization were inert liquid hydrocarbon, preferably a Hexanschnitt having a boiling range of 63 ° C to 80 ⁰ C, called. Using such diluents, however, it is not possible to produce pulverulent polymers of ethylene and butene- (I) with densities of about 0.900 g / cmr to about 0.930 g / cm '. Instead, the polymers are obtained as lumps and lumps and cannot be handled in technical equipment.

In contrast, it has now been found that low-density copolymers of ethylene and butene- (I) can also be used as free-flowing Powder with relatively high bulk densities can be produced if liquid butene- (l) is used as the inert diluent, which may also contain other inert, saturated and / or unsaturated C. hydrocarbons.

The invention therefore relates to a process for the production of pulverulent thermoplastic copolymers from ethylene and butene- (l) with densities of about 0.900 g / cm · ⁵ to about 0.930 g / cm ^, good flowability of the powder, average

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sized grain diameters up to 1 000 pm and practically without extremely fine particles by polymerization of ethylene and butene (l), optionally in the presence of hydrogen, in inert liquid hydrocarbon at temperatures between 50 ⁰ C and about 95 ⁰ C and pressures of 10 bar to 100 bar, preferably 20 bar to 60 bar, according to a discontinuous or continuous process using Ziegler catalysts, produced in inert liquid hydrocarbons by reacting chlorine- and alkoxy-containing vanadyl (v) compounds with organoaluminum compounds, separating off the insoluble reaction product and activating it with organoaluminum compounds, where the vanadyl (V) compound is a reaction product of vanadyl (V) chloride and a vanadyl (V) alcoholate in molar ratios of 1: 2 to 2: 1 or directly the reaction product of vanadyl (v) chloride with an alcohol, preferably ethanol, propanol (l), butanol (l) in molar ratios from 1 to 2 to 1 to 1 and as alu Organomine compound for the reduction of ethylaluminum dichloride and / or diethylaluminum chloride, isobutylaluminum dichloride and / or diisobutylaluminum chloride in molar ratios of aluminum to vanadium compounds of 1 to 1 to 3 to 1 and the conversion of the vanadium compounds with the organoaluminum compounds with stirring with specific stirring powers of 0 1 to 20,000 watts / m ^, preferably 1 to 5,000 watts / m ⁵ , and activation with aluminum alkyl compounds of the formula AlR-, where R is hydrocarbon radicals with 2 to 8 carbon atoms, or with alkylaluminum sesquichloride and / or alkylaluminum dichloride , in particular ethylaluminum sesquichloride and / or ethylaluminum diehlorld, characterized gekennzeic h η et that one polymerizes in liquid butene- (l), optionally in the presence of other inert, saturated and / or unsaturated C. hydrocarbons.

According to the invention, polymerisation is preferably carried out using pure butene- (I). The commercial purity is 99 percent. According to the invention, however, a C ^ -

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Cut, which, for example, apart from butene- (1), trans- and cis-Duten- (2), Can contain isobutene, η-butane and isobutane. It is important that the admixtures are opposite to the polymerization catalyst behave indifferently. For example, the mixture should not contain any butadiene— (1,3), which has proven to be a catalyst poison. Of course, care must be taken to ensure that the polymerization for the desired Density of the copolymer in each case required molar ratio of butene (I) to ethylene is observed.

The method according to the present invention surprisingly offers the possibility of copolymers with the catalyst system known from Belgian patent specification 862,697 from ethylene and butene- (l) with much lower densities than those described in the Belgian patent, the polymers as a powder in the diluent incurred in suspension and after their separation from the suspension for further processing into plastic parts after the addition of the customary finishing auxiliaries are suitable, so that the otherwise necessary preparation of the polymers to granules can be omitted. Since very high conversions can be achieved with the catalysts used according to the invention, measures to remove the catalyst from the polymer can be dispensed with. As a result of their high molecular weights the low-density copolymers prepared according to the invention have excellent performance properties. So have produced from the copolymers produced according to the invention In addition to their high flexibility, which is required for some applications, pipes have high burst pressures and excellent Alternating flexural strengths. Injection molded parts show an excellent surface gloss and have no tendency to Shrinkage and warpage. From the copolymers produced according to the invention manufactured foils are characterized by their special impact resistance and elongation.

The method according to the present invention is illustrated by the following examples:

Examples 1-10

a) Catalyst production

122.3 g (705.7 mmol) of vanadyl (V) chloride and 172.3 g (705.7 mmol) of vanadyl (V) n-propoxide were combined in a 1.7 Hexanschnittes 63/80 ⁰ C under nitrogen Heated to 55 ^° C. for 2 hours. After cooling the mixture was ^ at 20 ⁰ C to 25 ⁰ C a solution of 358.2 g (2 822.8 mmol) in AthylaluminiumdiChlorid 1 ^ 3 1 of Hexanschnittes 63/80 ⁰ C in the course of 2 hours with stirring at added to a paddle stirrer and a specific stirring power of 126 watts / m ⁵ . The resulting suspension was then stirred for 2 hours at 55 ⁰ C with the same specific stirring power. After cooling, the solid was separated off and washed five times with 5 l each time of the hexane cut.

b) Copolymerization of ethylene and butene- (l)

K ml of a solution of triisobutylaluminum in hexane with a concentration of 100 g / l were pipetted into a 2 l steel autoclave under nitrogen. Under water cooling

! Treatment were 600 g of butene (l) over a 3 A molecular sieve

(Manufacturer: Union Carbide) pressed the filled cartridge into the autoclave. This was followed by the polymerization temperature heated up. To remove the nitrogen were

j vented k liters of gas through a gas meter. Then water

. pressed on the substance and then with stirring (1,000 rpm)

• len. A sluice was a suspension of the under

j a) described catalyst component with a concentration

tion of 10 g of solid per liter of hexane in the autoclave

j drained. After the polymerization time, during

which the polymerization temperature and the pressure were kept constant by adding ethylene, was on

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Cooled room temperature and the excess butene relaxed. More detailed information on the individual examples can be found in Tables 1 and 2 below.

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Table 1

Copolymerization of ethylene and butene- (l)

at Catalyst- P _H ² ^ total T t 1 the end Catalyst utilization cm '/ g density Rubble- game component 2 prey 180 at density ^ ' No. according to a) bar 4th kg polymer 230 23 ° C mg 1.5 bar ⁰ C H 4th G g catalyst solid 190 g / cm- ⁵ 1 10 1.5 33 75 4th 104 10.4 500 0.925 0.264 2 15th 1.5 33 75 20th 151 10.1 330 0.915 0.306 3 10 0.5 33 75 4th 16O 16.0 250 0.917 0.301 4th 10 o, 5 33 75 1 219 21.9 220 0.909 0.265 VJl 10 0.5 28 75 4th 131 13.1 250 0.904 0.355 6 * ' 15th 1.5 14th 75 4th 120 8.0 280 0.916 0.365 7th 10 1.5 36 60 217 21.7 36O 0.920 0.320 8th 10 1.5 36 55 184 18.4 0.924 0.300 9 10 1.5 36 55 336 33.6 0.926 0.315 10 10 36 50 312 31.2 0.930 0.315

1) Viscosity number according to DIN 53728

2) DIN 53479

3) DIN 53468

4) Instead of 66Ο g of butene- (l) is a mixture of 103 g of butene- (l), 148 g of butene- (2), 210 g of trans-butene- (2) and 234 g of η-butane were used been.

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Table 2

Properties of the copolymer from Example 2

characteristic M e ß m e t h ο d e DIN 53735 DIN 53479 unit value Viscosity number J ISO / R
1191-70 DIN 53728
Sheet 4 DIN 53460
Test procedure
ren A / 50 DIN 53455
Feed
speed
age V
Test rod 4
2 c * 3 _{/ g} 230 Molecular data Differential scanning
Calorimeter
dito DIN 53456
(H 358/30) Middle Molec
large weight M Solution viscosity
c = 0.001 g / cm * ISO / R
1183 DIN 53505 90,000 Middle Molec
large weight H " ISO / R
527, pre
thrust-
dizzy
ability C
Test rod
according to fig. DIN 53 ^ 5 130,000 ISO 2039
(H 358/30) 20th IR analysis
C = C / 1000 C
vinyl
trans
Vinylidene
CII ^ / 1000 C 0.12
0.07
0.06
46.1 Melt index
MFI 190/5 ISO 1133
Procedure 5 ISO / R 537
Method a g / 10 min 3.1 Vicat softening
temperature ISO 306-
1974 ⁰ C 85 Melting range
Heat of fusion Beginning ⁰ C
Max. ⁰ C
End ° C
J / g 75
125
135
60 Density at 23 ° C g / cm ⁵ 0.915 Yield stress
Tear resistance
Elongation at break N / mm ²
N / mm ² 7th
16
850 Ball indentation hardness N / mm ² 12th Shore A hardness Shore A
Hardness-
units 95 Shear modulus
at 23 ⁰ C N / mm ² 140

Gel permeation chromatographic analysis

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Example 11

a) inventive copolymerization of ethylene and butene- (l)

The procedure of Example 10 was repeated. Deviating from this, a mixture of 79 g of butene- (l), 228 g n-butane, 214 g trans-butene- (2), 148 g cis-butene ~ (2) used. The amount of the solid catalyst component was 44 mg. The polymerization was already after one Hour canceled. 55 g of a free-flowing powdery polymer were obtained. The properties are listed in Table 3.

b) Comparative experiment

The procedure was as under IIa) but with the difference that 63/80 ⁰ C was used as a diluent of hexane. The amount of butene (I) used was 72 g, the ethylene partial pressure as in Example 11a) 4.5 bar. The yield of polymer was 79 g and consisted of coarse chunks or lumps.

Table 3

example Viscosity density Bulk density Trickle speed number J DIN age DIN 53728 53479 DIN 53468 DIN 53492 cm ^ / g g / cm ⁵ g / cm ⁵ era "Vs lla 130 0.920 0.335 4.7 * 11b
Comparison
attempt 230 0.922 not be
tunable not be
tunable

* Diameter d of the outlet opening of the trickle funnel: 10 mm

Example 12

The procedure was as in Example 1. Instead of triisobutylaluminum, however, tri-n-octylaluminum was used as a cocatalyst. 2.2 ml of a solution in hexane with a concentration of 167 g of tri-n-octylaluminum per liter were used. The amount of solid catalyst component was 20 mg, the hydrogen partial pressure was 1.0 bar, and the total pressure was 33 bar. Polymerization was carried out for h hours at 60 ^° C. The polymer consisted of a free-flowing powder. Further information can be found in table k .

Example 13

The procedure was as in Example 12. Instead of tri-noctylaluminum, however, diethylaluminum chloride was used, namely 2.2 ml of a solution in hexane with a concentration of 112 g of diethylaluminum chloride per liter. The polymer consisted of a free-flowing powder. Further information can be found in table h .

Table k

Copolymerization of ethylene and butene- (l)

at Cocatalyst the end Catalyst- J ¹ ) Density ² ^ Rubble- game prey exploitation at density ⁵ ' kg polymer 23 ° C gcatalyst— "7. No. G solid cm-yg g / cm- ⁷ g / cm- ' 12th Tri-n-octyl
aluminum 180 8.5 390 0.900 0.325 13th Diethylalu
minium chloride 19 ^ 8.7 3 ^ 0 0.915 0.265

1) Viscosity number according to DIN 53728

2) DIN 53 ^ 79

3) DIN 53 ** 68

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Claims (1)

Process for the production of powdered thermoplastic Copolymers of ethylene and butene - (l) Claim Process for the production of pulverulent thermoplastic copolymers from ethylene and butene- (1) with densities of about 0.900 g / cm ^ to about 0.930 g / cm ', good flowability of the powder, mean grain diameters up to 1000 μm and practically no fine grain fraction by polymerization of ethylene and Bu ⁺ en- (l), optionally in the presence of hydrogen, in inert liquid hydrocarbons at temperatures between 50 ⁰ C and about 95 ⁰ C and pressures of 10 bar to 100 bar, preferably 20 bar to 60 bar, after discontinuous or continuous process using Ziegler catalysts, produced in inert liquid hydrocarbons by reacting chlorine- and alkoxy-containing vanadyl (v) compounds with organoaluminum compounds, separating off the insoluble reaction product and activating it with organoaluminum compounds, the vanadyl (V) compound being a reaction product of Vanadyl (v) chloride and a vanadyl (v) alcoholate in molar ratios vo n 1 to 2 to 2 to 1 or 21/0108 ^0RIGiNAL inspected -., · ■. ": ;; ■ 2847386 directly the reaction product of vanadyl (v) chloride with an alcohol, preferably ethanol, propanol- (l), butanol- (l) in Molar ratios from 1 to 2 to 1 to 1 and, as an organoaluminum compound for reduction, ethylaluminum dichloride and / or diethyl aluminum chloride, isobutyl aluminum dichloride and / or diisobutylaluminum chloride in molar ratios of Aluminum to vanadium compounds from 1 to 1 to 3 to 1 used and the reaction of the vanadium compounds with the organoaluminum compounds with stirring with specific Mixing capacities from 0.1 to 20,000 watts / m- ^, preferably 1 to 5,000 watts / m-% is made and the activation with Aluminum alkyl compounds of the formula AlR-, in which R is hydrocarbon radicals with 2 to 8 carbon atoms, or with alkyl aluminum sesquichloride and / or alkyl aluminum dichloride, in particular ethyl aluminum sesquichloride and / or ethyl aluminum dichloride takes place, marked by this, that one in liquid butene (I), optionally in the presence of other inert, saturated and / or C. unsaturated hydrocarbons, polymerized. 030021/0108